Process for obtaining beryllium and beryllium alloys



Patented Mar. 12, 1940 vUNETED STATES PROCESS FOR OBTAINING BER-MUM ANDBERYLLIUM ALLOYS Carlo Adamoli, Milan, Italy, assignor tc PerosaCorporation, Wilmington, Del., a corporation of Delaware No Drawing.Application May 24. 1987, Serial No. 144,411. In Italy June 6, 1986 isClaims.

The present invention relates to a process for directly obtaining in asingle operation starting from compounds containing beryllium,beryllium, more particularly in the state of alloys with one or morealloying elements capable of alloying with beryllium, as well as, ifdesired, in the state of pure metallic beryllium.

It is known how many difliculties of chemical, thermal and technicalnature are presented by m the problem of effecting by direct reactionstarting from beryllium compounds, the production of beryllium alloyswith determined contents, in particular of a high beryllium content, aswell as of pure beryllium.

It has never been possible up to now despite numerous attempts. toeffect with industrial yields the production of beryllium and of itsalloys by thermo-chemical treatment of beryllium compounds.

The dimculties of chemical and thermal nature met with in decomposingberyllium compounds arise in particular from the fact that the exchangereactions which take place are very quickly checked or give rise to theformation of products which hinder them being carried out under theconditions in which it is desired to operate. From the technical pointof view these difiiculties are increased by the lightness of theberyllium which tends to float upon the slag and to be maintainedseparate from any heavy metal present, by the high melting point ofberyllium and by its great tendency to be oxidised or to form carbides.

In the presence of all these difllculties it has 35 been proposed to usefor replacing thermo-chemical treatments, electrolytic processes. butnone the less without arriving. by reason in particular of thenecessarily very high cost of the manufacture, at obtaining industrialresults and being able to effect this manufamture upon an industrialscale.

One is thus brought back to the thermo-chemical method for theproduction of beryllium and its alloys by treatment with a decomposingbivalent metal such as magnesium. of a fluorinecontaining compound ofberyllium, that is a double fluoride of beryllium and an alkali metalsodium) less rich in sodium fluoride than the double fluoride BeFaZNaF'.

..u The practical impossibility in fact had been established which ismet with in operating with the double fluoride according to the reactionBeFz.2NaF+2Mg=Be+2Na+2MgFz which is rendered explosive by reason of theliberation of sodium and this is the reason in particular why instead ofthe double fluoride BeFz.2NaF the complex fluoride BeFaNaF is treatedaccording to the reaction:

This reaction would seem to be rendered possible here by the fact thatthe sodium fluoride and magnesium'fiuoride formed are present in a ratiosuch that the reversibility of the reaction which would lead to thesetting free of sodium is prevented. However, as seen, the reaction thusefiected does not lead to the liberation in the metallic state of morethan half the beryllium contained in the compound treated, the otherhalf of beryllium remaining in the residue in the form of a complexcompound from which the said beryllium may be extracted for example inthe form of double fluoride. From this there results a large diminutionof the yield of the operation and a corresponding increase in the netcost of the manufacture.

Thus the processes known up to now have not permitted a solution of theproblem of the industrial manufacture of beryllium and its a1- loys.

This problem is solved nevertheless in a simple and practical manner bythe present invention and that in conditions where there is eflected ina direct and complete manner and with a high yield practically reaching100%, the production of beryllium, more particularly in the state ofalloys with predetermined contents, whatever these may be, and inparticular with a beryllium content above 25% or as high as is desired.

Although none of the known processes permitted practically completereactions to be efiected, the new process which forms the subject of theinvention permits such quantitative reactions to be regularly eflectedand obtained, while allowing to be obtained with practically totalmaximum yield alloys of beryllium with determined contents starting fromany compound of beryllium capable of being decomposed by a metal ormetalloid whether these compounds are contained in ores or obtained bytreatment of these latter and more particularly starting fromfluorine-containing compounds of beryllium.

The invention consists for this purpose in its most general aspect ineflecting an integral displacement oi the beryllium from its compoundsand notably from its fluorine-containing compounds by means of metals ormetalloids capable of liberating the beryllium therefrom, by causing toact a quantity of this metal or metalloid such that it correspondssubstantially stoichiometrically to the quantity of beryllium containedin the compound treated so as to displace from it up to the whole of theberyllium, by a reaction of tion the metals or metalloids which arecaused to act to displace, due in particular to their electro-positivecharacter, which is more electropositive than beryllium, the berylliumfrom the compounds treated, will be designated under the termdecomposing elements (metals or metalloids).

The complete exchange reaction is eiiected in general by a simple fusionoperation. For this purpose one may mix for example in the cold thereacting materials: compounds of beryllium and decomposing metals ormetalloids and simply melt them together, this single fusion operationensuring the complete chemical transformation by double exchange whichis effected if the .stoichiometrical proportions have been used, withouthaving recourse to any special operating means.

The operation may be efl'ected advantageously in an electric inductionfurnace such as a high frequency furnace, but it is obvious that allknown operating methods and apparatus which are suitable may equallywell be employed.

As compounds of beryllium to be treated there may be used as has beenindicated above any compounds, or even ores containing them, capable ofbeing decomposed by the process according to the invention. There areutilised, however, more particularly fluorine-containing compoundsconstituted either for example by beryllium fluoride or by a doublefluoride of beryllium and an alkali metal called in general berylliumand akali double fluoride (for example a double fluoride of berylliumand sodium) or by a mixture of simple beryllium fluoride, and berylliumand alkali double fluoride; it should be stated that the berylliumfluoride which is utilised is an anhydrous fluoride practically freefrom oxide, in contrast to the usual products which comprise asubstantial proportion of beryllium oxide, not fusible at thetemperature of the operation and non-reducible, not permitting inconsequence the whole of the beryllium to be extracted; the berylliumfluoride is conveniently employed in this form in many cases by reasonin particular of the fact that it considerably increases the fusibilityof the slags which are formed thus facilitating the separation of themetallic products and the slags.

According to the invention the fluorine-containing compound of berylliumis advantageously treated in the presence of or in admixture with afluoride of another metal, preferably at least bivalent, such as thefluoride of magnesium or of an alkaline earth metal.

The interest in operating in the presence of such a fluoride of analkaline earth metal or magnesium, according to the invention, inparticular in the case where a beryllium and alkali double fluoride istreated, may be explained by the fact that this alkaline earth or otherfluoride acts as a neutralizer preventing the setting free, during thereaction, of the alkali metal of the double fluoride treated, and, dueto the fact that Just the necessary stoichiometrical proportion of themetal or metalloid which acts as decomposing element is caused to act,there is thus eflected an integral displacement of the beryllium of thecompound treated without danger of setting free alkali metal (forexample sodium).

Thus, for example, in the case where the double fluoride of berylliumand sodium is treated in the presence of calcium fluoride the operationfollows the recation:

the (CaFa) added acting as a neutralizer due to which all the sodiumremains fixed by the fluorine in the form of NaF.

By thus utilising for extracting all beryllium from a molecule ofBeNazF4, a single molecule of Mg (instead of two molecules of Mg whichwould necessitate the corresponding reaction when liberating sodium)there has been effected under the optimum conditions the quantitativereaction:

To sum up, the utilisation of a fluoride of a bivalent metal, such as analkaline earth metal or magnesium, in the presence of which theoperation is carried out, prevents the setting free of sodium or otheralkali metal which the compound of beryllium treated may comprise, dueto the fact that it tends to decompose preferentially to sodium fluorideand by its tendency to set free fluorine it favours a reaction whichensures the fixation of the fluorine by the sodium in the form of NaF inparticular.

In the case of obtaining beryllium alloys it may be of interest to addmoreover to the slags alkali or alkalinised salts which are notoxygenated, such for example as fluorides and chlorides, in order tomodify the fusibility of the slags according to the nature of the alloysto be obtained.

The proportions of reacting materials to be employed according to theinvention may be determined in advance by calculation to efl'ect thedesired quantitative reactions.

If: A, is the quantity of beryllium compound treated;

13, the quantity of beryllium alloy to be obtained;

a, the berylliumcontent of the beryllium compound treated;

b, the beryllium content of the alloy to be obtained;

C, the quantity of decomposing metal or metalloid to be caused to act;

E, the chemical. equivalent of beryllium;

e, the chemical equivalent of the deccmposing metal or metalloidemployed, the necessary proportions of reacting materials, which shouldbe approached as closely as possible are the following:

The quantity A of thecompound of beryllium to be decomposed isdetermined by the expression:

The quantity C of the decomposing metal or metalloid necessary to beemployed is determined by the equation:

One may thus say that there is caused to act upon the beryllium compound(which is in quantity equal to the quantity of beryllium to be obtaineddivided by the beryllium content of this compound) a quantity ofdecomposing metal or metalloid which is practically equal to thequantity of beryllium to be set free multiplied by the ratio of thechemical equivalents of the beryllium and of the decomposing metal ormetalloid.

As decomposing metals or metalloids to be caused to act upon theberyllium compounds in particular the fluorine-containing compounds tobe decomposed whatever they may be, there may be utilised advantageouslyeither singly or in a state of mixture as desired one or more metalsmore electro-positive than the beryllium to displace the latter from itscompounds: the best results are obtained by employing one or more metalsof the group comprising the alkali metals (for example Na, K, Li) thealkaline earth metals (for example Ca, Ba, Rb, Sr, Ce) and magnesium;the metals which are more clearly electro-positive than beryllium are ofthe greatest importance. However, very satisfactory results havelikewise been obtained with less electropositlvemetals such as aluminiumor even with metalloids playing the part of electro-positive elementssuch as silicon, boron, or carbon.

In certain cases it may be of interest to introduce the decomposingmetals or metalloids in the state of metallic compounds or to operate inthe presence of metallic compounds so as to be able to bring in thecourse of the operation the decomposing element into the state of themetal or metalloid.

. In the case in particular where it is desired to utilise sodium asdecomposing element, to avoid.

the tendency to produce ebullition which is ex hibited by sodium alone,it is of interest to cause this metal to react in the presence ofmetallic compounds for which the sodium has a chemical aflinitysuflicient to allow by the formation of an eutectic mixture for examplea practically quantitative reaction to be efiected without difficulty.

Amongst the bivalent metals besides the alkaline earth metals magnesiumis particularly advantageous as decomposing metal. When magnesium forexample is caused to act upon the double fluoride of beryllium andsodium the decomposition of the latter takes place first at about 900 C.according to an intermediary reaction giving a double fluoride ofberyllium and magnesium for example:

then, according to a second double exchange'reaction (at about 1100 C.)which is much more active than the first and takes place according tothe reaction:

By introducing into the mixture an excess of sodium salt with themagnesium fluoride which is formed a mixture of low melting point isformed which facilitates to a large extent the agglomeration of theberyllium into a compact state.

As has been indicated above. there may likewise be caused to act a metalless electro-positive than beryllium such as aluminium. This latter infact reacts in a complete manner upon the beryllium contained influorine-containing compounds comprising beryllium fluoride, when thereis used for example a mixture of magnesium fluoride and berylliumfluoride, the magnesium fluoride being present in quantity at leastchemically equivalent to that of the beryllium fluoride.

The reaction then takes place according to the equation:

This reaction takes place even when the mixture of fluorides comprisesanother element, for example oxygen, provided that the ratios ofequivalents mentioned above are maintained.

In the case when a metalloid such as silicon is used as decomposingelement this silicon may react upon the fluorine-containing compounds ofberyllium in well determined conditions in the same manner as a metalmore electro-positive where M represents a bivalent metal. The means forensuring the stability of the fluosilicate which is formed by thereaction are very simply effected practically; silicon will be used, forexample, for this purpose in the state of a eutectic mixture with ametal which is at least bivalent.

To obtain by the process according to the invention alloys of berylliumwith aberyllium con- .tent varying as desired betweeni less than 1%- andup to nearly 100% it is suitable to cause to act the decomposing metalsor metalloids in the presence of the metal or metals or possiblymetalloids to be alloyed with the beryllium or even metallic compoundscapable of providing during the course of the reaction the alloyingelement or elements.

The desired contents of the final alloy to be obtained are obtained bythe fact that there is employed a quantity of alloying element exactlyproportioned to the proportion of this body that the final alloy shouldcontain.

In general the decomposing metals or metalloids are caused to act eitherin the presence of the element or elements to be alloyed with theberyllium or in the state of mixtures or alloys with them.

As elements capable of being employed moreparticularly as elements ofthe decomposing alloys, one may use in particular one or more of thefollowing elements to obtain binary alloys or alloys with moreconstituents: copper, iron, nickel, cobalt, tungsten, molybdenum,chromium, vanadium, boron, titanium, manganese, zinc, silver, tin,thallium, bismuth, lead, cadmium, uranium, lithium, calcium, magnesium,aluminium, silicon, phosphorus, carbon, gold, platinum.

Inasmuch as concerns efiecting the operation proper this operationconsists in a general manner in bringing into contact the reactingmaterials for example in the cold, partly or wholly, in mixing them ifdesired and in melting them together for example in a crucible; it maybe of interest for example when the temperature of fusion of the slaghas been attained, to effect an agitation by any known means for exampleby electrical or mechanical agitation, and the alloy or beryllium isfinally allowed to separate from the slag formed.

For collecting thus the final product to be obtained as easily aspossible without losses, and in the maximum state of purity, it has beenascertained that it is of interest to operate preferably in conditionssuch-due in particular to the careful choice of the reacting materialsemployed that this final product (beryllium alloy or if desired metallicberyllium) is obtained in the form of a compact mass which separates byitself from the other products of the reaction forming in particular theslag.

This result may be obtained in particular by causing to act mixtures oralloys, of the decomposing element or elements with the element orelements to be alloyed with the beryllium, which are such that they havea weight substantially different from that of the compound of berylliumtreated, so that after admixture the alloy produced has likewise aweight substantially different from that of the slag which is formed andthus separates from it in the form of a compact product.

One may, for example, for this purpose cause a decomposing alloy to actinitially which is heavier than the compound of beryllium treated in themolten state and which gives rise to an alloy which is heavier finallythan the slag formed which in general has a specific gravity which islower if it is brought, for example by agitation of the said slag, intoan advanced state of division.

Conversely when light alloys of beryllium are made the operation may beeffected by employing decomposing mixtures or alloys which form a slagclearly heavier than the product of the reaction; the alloy thencollects above the slag.

According to the present invention it has been observed that theformation of beryllium alloys with desired contents is largelyfacilitated when the decomposing element (metal or metalloid capable ofdecomposing the beryllium compound) and the metal or metals (or possiblymetalloids) to be alloyed with the beryllium are employed in the stateof a mixture melting at a relatively low temperature and moreparticularly at a temperature below the melting point of its components.In the case of a metal to be alloyed with the beryllium there isadvantageously employed a mixture or an alloy of the decomposing elementand of this metal, associated in relative proportions which approach orcorrespond to the composition of the eutectic mixture.

The use of such a mixture with a low melting point with respect to itscomponents, formed in general by metallic elements which are moreelectro-positive than beryllium with metallic elements lesselectro-positive than this latter, constitutes a very practical meansfor facilitating the exchange reaction which is effected in generalbetween the more electro-positive element and the beryllium of thecompound treated. It is only in certain cases by this means that theformation of alloys is rendered practically possible for a maximumyield. It is sufficient in these conditions to operate at a temperaturewhich need only be sufficient for the reacting materials and theberyllium alloy produced to be in the molten state.

In order to obtain more particularly light alloys of beryllium, forinstance with aluminium, binary alloys may be used or alloys containingmore than two metals which have the state of mixtures with a meltingpoint which is low with respect to the components and which react bydouble exchange upon the beryllium compounds.

One may operate under such conditions that the temperature does notexceed in any case the melting point of the eutectic or eutectoldmixture formed by beryllium with the other metals to be alloyed with theberyllium.

There are obtained in particularly advantageous conditions the lightalloys of beryllium by utilising as reactive alloy 8. eutectic alloywith a low melting point; it happens that the beryllium during and inproportion to its formation passes into the state of the liquid alloy tobe obtained and the melting point of this new alloy increases with thequantity of beryllium present, but however high is the content ofberyllium which it is desired to obtain in the final product, theberyllium set free alloys during and. in proportion to its formation, amthe temperature to be reached remains always very much lower than thatwhich is necessary for the melting of pure beryllium (about 1285).

In all cases the exchange reaction is effected at a temperature which isalways relatively low and the lower, all other things being equal, thelower the melting point of the mixture employed for decomposing theberyllium compound with respect to the melting point of its components.The important thing is that the beryllium should be itself set free at atemperature which is always lower than the melting point of this metalbut it does not pass into the solid state by reason of the fact that itfinds for alloying with it during and in proportion as it is formed theother element or elements in the liquid state which form with it thealloy of beryllium to be obtained. In many cases the element of thealloy forms thus with beryllium an alloy constituting itself a eutecticalloy. The temperature of the reaction and duration of the operation arereduced to a particularly great extent when in order to. ensure thedouble exchange reaction the decomposing element is employed preciselyin the state of a eutectic alloy with the or one of the alloyingelements.

The utilisation of a eutectic can only conduce it is true to theformation of alloys of beryllium the contents of which only vary withinrelatively narrow limits. To obtain, however, all the possible range ofthe beryllium alloys the eutectic is caused to act in the presence of adesired supplementary quantity of alloying element. It is suflicient toadd for this purpose the supplementary quantity calculated exactly inadvance of the alloying metal of the eutectic or if desired of one ormore alloying metals. In the normal conditions of the operation theseadditions 'of alloying element 0.xelements do not exercise-any influenceupon the action of the decomposing eutectic alloy and in consequence onearrives at fusing without difliculty the alloying elements in desiredproportions predetermined in the same operation with the alloy ofberyllium formed by double exchange with the eutectic employed. Thereaction will be effected more correctly if the decomposing eutecticalloy by the conditions of contact and/or temperature is more incondition to act upon the compound of beryllium to be de-- composedbefore its eutectic character is substantially modified by interventionof the supplementary quantity of alloying element.

One may also effect the previous formation of the eutectic alloy in thebody itself of the mixture which is subjected to the operation, byintroducing in the free state a part of the metal which should form theeutectic with the reacting decomposing element.

aicaacs There are indicated in the following, various non-limitingexamples corresponding to typical cases, ofeflecting the processaccording to the invention.

Example 1 previously prepared by means of lithium and' nickel inpowdered form having a nickel content of17.75% are caused to react uponit. The mixture of this decomposing alloy and the double fluoride issubjected to gradual heating up to the melting point of the nickel byutilising a crucible protected by means of beryllium oxide (glucine) andwell'closed. The alloy is subjected to regular agitation while heatingit until the reaction is achieved and practically complete. There iscollected in the base of the crucible about 9 kgs. of a beryllium alloyin the molten state in the form of a compact and homogeneous masscontaining 74-76% of beryllium and 26-24% of nickel. The metallic alloythus collected may be decanted by pouring by means of any known process.The

slag which is formed is constituted by a double fluoride of lithium andsodium, it may be caused to undergo any suitable known treatment forrecovering the lithium therefrom.

Example 2 Production of a beryllium nickel alloy by means of an alloy ofmagnesium and nickel.

. composed, which was the double fluoride of beryllium and sodium. Thusthere has been obtained by a single operation of fusion in a cruciblethe desired alloy of beryllium and nickel in the form of a well compactregulus at the bottom of the crucible. This alloy had the followinganalysis: Be: 41.8% Ni:58.2%. It melts at 1100" C. that is to say about185 below the temperature of the melting point of beryllium.

Example 3 Production of a Be-Ni alloy with 25% of Be by means ofaluminium and nickel.

With 110 kgs. of an intimate mixture pulverised in the absence of air ofberyllium fluoride and magnesium fluoride in equimolecular quantities,l8 kgs. of aluminium filings and 27 kgs. of nickel filings areincorporated. The mass is strongly compressed in a graphite cruciblewhich is covered and introduced into a muille furnace without air at atemperature of 1200 C. This temperature is maintained for a period whichvaries according to the heat capacity of the muille itself. Thus, if thetemperature. of 1200 C. can be attained in 35-40 minutes it willbemaintained thus for an hour. Then it is cooled, the slag is poured awayand there is thus obtained a Be- Ni alloy with 25% of Be and of Ni.

Example 4 Production of a beryllium copper alloy with 25% or Be by meansof magnesium and copper.

' The reacting substances are introduced in the cold by putting into agraphite crucible with 9. capacity of about 10 litres, that is to say atthe bottom in large portions 4.250 kgs. of an alloy of magnesium andcopper with 20% of Cu, and above it 6 kgs. of anhydrous and oxide-freeberyllium fluoride, compressing it strongly; above again there is placed1 kg. of the double fluoride of sodium and beryllium and again in large.

portions 2.875 kgs. of electrolytic copper. After having covered thecrucible with a graphite cover it is introduced into a muifie withoutcirculation of air and the temperature is rapidly raised to 900 C. Thistemperature :is maintained for 20-25 minutes and is then caused rapidlyto rise to 1200 C. The alloy is alloyed to deposit-and poured, thusseparating the slag, and there is thus obtained 4.927 kgs. of an alloywith about 25% of Be and 75% of Cu.

Example 5 Production of a Be-Cu alloy with of Be.

In a graphite crucible coated with BeO and provided with a cover, 3.1kgs. of metallic magnesium are introduced upon a mixture of 6 kgs. ofanhydrous oxide-free beryllium fluoride with 3% of copper fluoride. Thetemperature is maintained for 30 minutes at 900 C. then it is raised to1200 C. and maintained there until the fused mass is calm, then it ispoured into an ingot mouldseparating the slag. There is thus ob tainedabout 1.250 kgs. of a Be-Cu alloy with 83% of Be. The calculation showsthat the quantity of Be contained in the alloy should be about in placeof 83% as pointed out. This difference is due to the fact that, theoperation having been made on a small mass-of alloy, a notable quantityof Be remains incorporated with the slag (this quantity beingsubstantially inversely proportional to the mass treated). The Be thusremaining in the slag will be recuperated in a subsequent operation byadding the slag to the substances to be treated.

Example 6 Production of a beryllium iron alloy by means of an alloy ofcalcium and iron in a high frequency induction furnace.

In a crucible protected by means of beryllium oxide in order to eflectthe operation by heating by induction 43 kgs. of an iron calcium alloywith about 18% of calcium comminuted into portions is placed, and uponthis molten alloy ischarged 10 kgs. of anhydrous oxide-free berylliumfluoride. The atmosphere of the crucible is maintained fed with hydrogento ensure the elimination of air. The temperature is raised up to1150-1200 C. and maintained at this for about half an hour so as tomaintain the mass in a state of fusion with agitation. After havinginterrupted the action of the inductive field and ceased theintroduction of hydrogen the slag is poured away and the metal is poureddirectly into ingots. There is thus obtained 37 kgs. of an alloy with4.8% of Be and of Fe.

Example 7 Production of a beryllium iron alloy with 40% of Be byutilising silicon as decomposing element..

metallic silicon containing 95% of Si and 5% of Fe in pieces. The massis covered by means of electrolytic iron in small pieces and compressedin a crucible of beryllium oxide or magnesia or even graphite coatedinside with magnesia or beryllium oxide. Above the mass a layer ofsodium fluoride mixed with fluorite and large pieces of electrolyticiron is laid. The crucible is placed in a muflle furnace slowly raisingthe temperature to 1400 C. The mass is then allowed to rest and ispoured separating the slag. An alloy of 60% Fe and 40% Be with smallquantities of silicon is obtained.

Example 8 Production of a beryllium iron alloy with 9% of Be by means ofa eutectic alloy of aluminium and iron.

Into the crucible of an induction furnace 7.5 kgs. of a eutectic alloyof aluminium and iron melting at 1160 is introduced. Above it arecompressed kgs. of a mixture of beryllium and magnesium fluoridecontaining 7.5% of beryllium and above this mixture 2.0 kgs. ofelectrolytic iron. The temperature is rapidly brought to 1180 C. andmaintained constant for 45-50 minutes. The material is poured into amould and there'is thus obtained 7.7 kgs. of an alloy of iron andberyllium with 9% of Be melting at 1155 0.

Example 9 Production of a ferrous alloy of beryllium and chromium,unattackable by acids.

In a crucible protected by means of BeO and provided with a perforatedcover through which passes a tube also of BeO for the introduction ofhydrogen there is placed 10 grams of a ferrous alloy with 21.5% ofchromium and 8.5% of nickel in large pieces; upon these there iscompressed a homogeneous mixture of 7 kgs. of

double fluoride of beryllium and calcium obtained starting fromequivalent quantities of the two fluorides and 8.50 kgs. of powderedsilicon (containing 95% of pure silicon). The whole is covered with athin layer of quick lime and fluorite. The crucible being thus preparedit is introduced into an induction furnace and while the temperaturerises rapidly hydrogen is introduced. At the end of 15-20 minutes ofvery active fusion it is allowed to cool, the slag is poured away andthe metal is poured into a mould for example. There is obtained thus10.5 kgs. of a special alloy of iron with 20.5% of Cr, 7.75% of Ni and4.75% of Be.

Example 10 Production of a silver beryllium alloy by means of an alloyof aluminium and silver.

melts at 558. By raising the temperature for an hour up to 1100 there isobtained after having poured into ingot moulds, about 555 grams of analloy with 18% of Be and 82% of silver melting at 880-1075 0.

Example 11 Production of light alloys constituted by binary alloys ofberyllium and aluminium.

By operating in conditions like those indicated above there may beadvantageously used as decomposing alloys, known eutectic alloys ofmagnesium and aluminium containing respectively 40 and 70% of Mg. 60 andof Al each of these alloys melting at a temperature of 460 C. In thesetwo cases light alloys are obtained containing 11% of Be and 89% of Aland of Be and 65% of Al respectively.

Example 12 Production of a light ternary alloy (Be-Al-Li) with 20-25% ofBe.

In a graphite crucible provided with a cover are introduced 2.100 kgs.of magnesium in cylinders having a purity of 99.8%. and above. wellcompressed, 1 kg. of the double fluoride of lithium and beryllium(BeFz2LiFl and 3 *kgs; of anhydrous'oxide-free beryllium fluoride. Abovethis 2.500 kgs. of aluminium in pieces is placed. After the crucible hasbeen covered it is introduced into a muille furnace and the temperatureis raised at the beginning-up to about 850 C. and maintained at this for20 minutes, then it is raised to 1250 C. When the molten mass is calmthe slag is allowed to deposit and the remainder is poured into ingotmoulds. In this way there is obtained about 3.300 kgs. of an alloy ofaluminium with 28.5% of Be and about 4.5% of lithium.

Example 13 Production of a light ternary alloy (Be-Al-Ll) with 40% ofBe.

By operating in conditions like those indicated above, there is meltedin 100 parts of molten sodium 10 parts of aluminium and 20 parts oflithium and the decomposing alloy thus formed is caused to react uponthe quantity of beryllium fluoride corresponding stoichiometrically tothat of the sodium employed. Finally there is obtained a Be-Al-Li alloyhaving substantially the following composition: 40% of Be, 40% of Li and2 of Al.

Example 14 Production of a light ternary alloy Be-Al-Cu.

The operation is performed in conditions similar to those indicatedabove by starting in order to constitute the decomposing alloy from 25parts of an alloy with 95% of aluminium and 5% of copper which isalloyed with 75 parts of calcium constituting thus a new alloy meltingat 500 C. This new alloy is then caused to act upon the quantity ofberyllium fluoride corresponding stoichiometrically to that of thecalcium employed. Finally there is obtained an alloy of 36% ofberyllium, oi aluminium. and 6% of copper.

Example 15 Production of pure beryllium.

In a graphite crucible coated with beryllium oxide and provided with acover there is introduced at the bottom 25 kgs. of pure magnesium inlarge cylindrical pieces and above it kgs. of anhydrous oxide-freeberyllium fluoride well mixed with 5% of fused sodium fluoride. Thetemperature is rapidly raised to 900 C. and maintained at this fortwenty minutes, and then the temperature is again raised up to 1290-1300C. and maintained there until the melt is calm. The free berylliumcondenses and floats on the molten slag. When the temperature has fallenbelow its melting point it may be withdrawn with an iron fork forexample. and allowed to cool in 7 the absence of air. Thus there isobtained.9 kgs. of beryllium oi. 99% purity ii the magnesium employedhas a purity of 99.85%.

In all the above the optimum conditions or operation have beendescribed, which lead to practically total extraction of the berylliumfrom the beryllium containing compound; however, it is obvious that nodeparture will be made from the scope of the invention by not strictlytulflllmg' these conditions but by applying the means with a margin ofapproximation such that a complete extraction of the beryllium is notobtained, that is to say for example that only a partial butnevertheless considerable extraction is efl'ected.

In the claims, the expression a metallic mass containing beryllium isintended to include beryllium alloys as well as pure beryllium.

I claim:

1. Process for directly obtaining a metallic mass containing beryllium,which consists in bringing together beryllium fluoride practicallyanhydrous and free from oxide and a quantity which practicallycorresponds stoichiometrically with the quantity of the berylliumcontained in the beryllium fluoride, of an element capable of reducingthe beryllium fluoride into beryllium, and in heating the whole untilthe reduction of the beryllium fluoride is substantially complete.

2. Process for directly obtaining a metallic mass containing beryllium,which consists in bringing together beryllium fluoride practicallyanhydrous and free from oxide and a quantity which practicallycorresponds stoichiometrically with the quantity of the berylliumcontained in the beryllium fluoride, of a metal belonging to the groupconsisting of the alkali metals, alkali earth metals, magnesium andaluminium, and in heating the whole until the reduction of the berylliumfluoride is substantially complete.

3. Process for directly obtaining a metallic mass containing beryllium,which consists in bringing together beryllium fluoride practicallyanhydrous and free from oxide and a quantity which practicallycorresponds stoichiometrically with the quantity of the berylliumcontained in th beryllium fluoride, of a metalloid belonging to thegroup consisting of silicon and boron, and in heating the whole untilthe reduction of the beryllium fluoride is substantially complete.

4. Process for directly obtaining a metallic mass containing beryllium,which consists in bringing together beryllium fluoride practicallyanhydrous and free from oxide and a quantity which practicallycorresponds stoichiometrically with the quantity of the berylliumcontained in the beryllium fluoride of an element capable of reducingthe beryllium fluoride into beryllium, and a metallic fluoride selectedfrom the group consisting of the earth alkali metal fluorides andmagnesium fluoride, and in heating the whole until the reduction of theberyllium fluoride is substantially complete.

5. Process for directly obtaining a metallic mass containing beryllium,which consists in bringing together beryllium fluoride practicallyanhydrous and free from oxide and a quantity which practicallycorresponds stoichiometrically with the quantity of the berylliumcontained in the beryllium fluoride, of an element capable of reducingthe beryllium fluoride into beryllium, and at least one alloying elementto be alloyed with the beryllium in quantity proportioned to the contentto be obtained in the final alloy,

and in heating the whole until the reduction of the beryllium fluorideis substantially complete.

6. Process for directly obtaining a'metallic mass containing beryllium,which consists in bringing together beryllium fluoride practicallyanhydrous and free from oxide and an alloy of \a reducing elementcapable of reducing the beryllium fluoride into beryllium and at leastone alloying element to be alloyed with the beryllium,

the reducing element being present in a quantity which practicallycorresponds stoichiometrically with the quantity of the berylliumcontained in the beryllium fluoride and the alloying element beingpresent in a quantity proportioned to the content to be obtained in thefinal alloy, and in heating the whole until the reduction or theberyllium fluoride is substantially complete.

7. Process for directly obtaining a metallic mass containing beryllium,which consists in bringing together beryllium fluoride practicallyanhydrous and free from oxide and a reducing element capable of reducingthe beryllium fluoride into beryllium and a compound of an alloyingelement to be alloyed with the beryllium capable of being reduced by thereducing element, the reducing element being present in a quantity whichpractically corresponds stoichiometrically with the quantity of theberyllium contained in the beryllium fluoride and with the quantity ofalloying element contained in said compound, and in heating the wholeuntil the reduction of the beryllium fluoride is substantially complete.

8. Process for directly obtaining beryllium alloys which consists inbringing together beryllium fluoride practically anhydrous and free fromoxide and a mixture of an element capable of reducing the berylliumfluoride into beryllium and of an alloying element to be alloyed withthe beryllium, the said mixture having a composition such that it meltsat low temperature with respect to its components, and the reducingelement being present in a quantity which substantially correspondsstoichiometrically with the quantity oi. beryllium contained in theberyllium fluoride, and in heating the whole until reduction of theberyllium fluoride is substantially complete.

9. Process for directly obtaining beryllium alloys, which consists inbringing together beryllium fluoride practically anhydrous and free fromoxide and an alloy of a reducing element capable of reducing berylliumfluoride into beryllium and of at least one alloying element to bealloyed with the beryllium, the said alloy having a composition near tothat of an eutectic alloy, and the reducing element being present in aquantity which substantially corresponds stoichiometrically with thequantity of beryllium contained in the beryllium fluoride, and inheating the whole until the reduction of the beryllium fluoride issubstantially complete.

10. Process as claimed in claim 9, in which a supplementary quantity ofalloying elements to be alloyed with the beryllium is added at the endof the operation to beryllium alloy obtained.

11. Process for directly obtaining beryllium alloys, which consists inbringing together beryllium fluoride practically anhydrous and free fromoxide and a mixture of an element capable of reducing the berylliumfluoridev into beryllium and of an alloying element to be alloyed withthe beryllium, the reducing element being present in a quantity whichsubstantially corresponds stoichiometrically with the quantity ofberyllium contained in the beryllium fluoride, and the said mixturehaving a specific gravity widely diflerent alloy collects by itself. inthe form of a compact from that of the beryllium and from that of themass under the said slag.

slag formed during the reaction, and in heating 13. Process as claimedin claim 11, in which the whole until the reduction of the beryllium themixture added to the beryllium fluoride is fluoride is substantiallycomplete. such that it gives rise to a slag which is heavier 5 12.Process as claimed in claim 11, in which the finally than the slagformed, so that the said mixture added to the beryllium fluoride is suchalloy collects by itself in the form of a compact that it gives rise toa slag which is lighter finally mass floating on the said slag. than theberyllium alloy formed, so that the said CARIQ ADAMOLI.

